Investigation of polynuclear Zr(IV) hydroxide complexes by nanoelectrospray mass-spectrometry combined with XAFS

Walther, Clemens; Rothe, Jörg; Fuss, Markus; Büchner, Sebastian; Koltsov, Sergei; Bergmann, Thorald
May 2007
Analytical & Bioanalytical Chemistry;May2007, Vol. 388 Issue 2, p409
Academic Journal
Polynuclear species of zirconium in acidic aqueous solution are investigated by combining X-ray absorption spectroscopy (XAFS) and nanoelectrospray mass spectrometry (ESI-MS). Species distributions are measured between pHC 0 and pHC 3 for [Zr] = 1.5–10 mM. While the monomer remains a minor species, with increasing pH the degree of polymerization increases and the formation of tetramers, pentamers, octamers, and larger polymers is observed. The high resolution of the mass spectrometer permits the unambiguous determination of polynuclear zirconium hydroxide complexes by means of their isotopic patterns. The relative abundances of mononuclear and polynuclear species present simultaneously in solution are measured, even if one of the species contributes only 0.1% of the Zr concentration. For the first time it has been directly observed that the hydrolysis of polynuclear Zr species is a continuous process which leads to charge compensation through the sequential substitution of water molecules by hydroxide ligands until doubly charged polymers dominate at conditions (H+ and Zr concentrations) close to the solubility of Zr(OH)4(am). The invasiveness of the electrospray process was minimized by using very mild declustering conditions, leaving the polynuclear species within a solvent shell of approximately 20 water molecules. [Figure not available: see fulltext.]


Related Articles

  • The Selectivity of Zirconium (IV) Iodomolybdate for Some Metal-Ammine Complexes. Rahman, Nafisur; Ahmad, Syed Taufeeq; Azmi, Syed Najmul Hejaz // IUP Journal of Chemistry;Sep2010, Vol. 3 Issue 3, p47 

    The sorption characteristics of Cu (II), Ni (II), Zn (II) and Cd (II)-ammine complexes on zirconium (IV) iodomolybdate, a cation exchanger, have been evaluated at different metal ion concentrations and pH values. The sorption capacity increases with increase in pH values, attaining a maximum...

  • Fibrillization of recombinant bovine prion protein (rec-PrP) in vitro. Grigoriev, V. B.; Kalnov, S. L.; Pokidyshev, A. N.; Tsibezov, V. V.; Balandina, M. V.; Gibadulin, R. A.; Verkhovsky, O. A.; Klimenko, S. M. // Doklady Biochemistry & Biophysics;May2008, Vol. 420 Issue 1, p112 

    The article presents a study that shows recombinant bovine prion protein (rec-PrP) during incubation in vitro at low pH values in the presence of denaturing agent is polymerized into fibrils whose structure, physicochemical properties, and high degree of polymorphism are similar to the...

  • Electrochemical properties of polyaniline-modified sodium vanadate nanomaterials. Reddy Channu, V.; Holze, Rudolf; Yeo, In-Hyeong; Mho, Sun-il; Kalluru, Rajamohan // Applied Physics A: Materials Science & Processing;Aug2011, Vol. 104 Issue 2, p707 

    Sodium vanadate nanomaterials were synthesized at different pH-values of a sodium hydroxide solution of vanadium pentoxide. Polyaniline-modified sodium vanadate nanomaterials were prepared at room temperature and at 3°C by a chemical polymerization method. The crystal structure and phase...

  • Formation of the Complexes of Ir(IV) and Pt(IV) with Xylenol Orange. Solovei, O. I.; Vrublevs'ka, T. Ya. // Materials Science;Jan/Feb2004, Vol. 40 Issue 1, p148 

    Reports on the formation of the complexes of iridium and platinum with xylenol orange. Control of the validity of the indications of the hydrogen ion concentration (pH)-meter using the buffer solutions with pH values; Presentation of the electron absorption spectra of the complexes of iridium...

  • Cationic poly(VCL–AETA) hydrogels and ovalbumin (OVA) release in vitro. Da-Qing Wu; Chih-Chang Chu; Fang Chen // Journal of Materials Science: Materials in Medicine;Dec2008, Vol. 19 Issue 12, p3593 

    The objective of this research is to explore the synthesis of a new family of water soluble polycationic copolymeric precursors that could be photo-crosslinked into hydrogels. The in vitro control release of ovalbumin protein (OVA) from this family of hydrogels was also studied to assess the...

  • Dependence of the third-order coefficients in Landau free energies for bcc-fcc structural... Ashida, Yuh; Yamamoto, Masahiro; Naito, Shizuo; Mabuchi, Mahito; Hashino, Tomoyasu // Journal of Applied Physics;8/1/1997, Vol. 82 Issue 3, p1072 

    Discusses various aspects of bcc-fcc structural transition on hydrogen concentration in zirconium hydrides. Obtaining expanded free energy for Bain tetragonal distortion; Bain triclinic distortion; Landau expression of free energies for Bain distortions.

  • Protein expression profile in the anterior cingulate cortex. Clark, D; Dedova, I; Cordwell, S; Matsumoto, I // Molecular Psychiatry;May2006, Vol. 11 Issue 5, p423 

    The article focuses on the expression of protein in a fresh human anterior cingulate cortex grey matter tissue sample. Proteins were separated in the first dimension by pH and by molecular mass in the second dimension. The grey matter proteome of the control group was compared with the...

  • Composition variation of papain-catalyzed esterification of a fibroin peptide mixture. Jeong, Jaeho; Lee, Shin-Young; Hur, Won // Biotechnology & Bioprocess Engineering;Aug2011, Vol. 16 Issue 4, p654 

    Composition variation of a complex peptide mixture under enzymatic transformation can be tracked by mass spectrometry (MS). In this report, papain-catalyzed esterification of fibroin peptides was investigated at the individual peptide level using liquid chromatography-mass spectrometry with...

  • Polymerization of fluoro-containing acrylic monomers: Determination of monomer conversion from absorption spectra in the near IR range. Kitai, M.; Molchanova, S. // Polymer Science -- Series A;Mar2012, Vol. 54 Issue 3, p195 

    For a series of polymers, including crosslinked polymers, based on fluoro-containing acrylic monomers, absorption coefficients are measured in the visible and near-IR ranges. The relationship between the intensities of observed absorption bands and the conversions of monomers during radical...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics